Nu-phosphatoarylenediamines



Patented Nov. 26, I

JosephB. Dickey and James G. McNally,

Y., minors to Eastman Kodak Com- 1 pany, Rochester, N.- Y,

ester, N.

g I Jersey Q '3 v N This invention relates and to a process for the preparation thereof,

s PATENT OFFICE n-rnosrna'roaarnmvnnmmns to aryl amino compounds well as to photographic developing agents comprising such aryl amino compounds. This application is a continuation-in-part of our copend- 301,467, filed October ing application, Serial No. 26, 1939. g

It is known that and p-phenylenediamines and some of their N-substituted derivatives act as photographic developers.

phenylenediamine is used as a photographic developing agent in color photography.

We have now found new phito derivatives of efllcacious photographic developers.

It is, accordingly, an object of our invention provide new arylenediamine. .derivatives and process for the phosphato and phosoand p-arylenediamin ,and have further found that these derivatives are preparation thereof. A further object is to provide new photographic developing agents comprising these new derivatives. Other objects will appear hereinafter. Our new arylenediamine represented by the following general formulas:

derivatives can be Roch-.

a corporation of New Drawing. Application March 4, 1943,

Serial No. 478,002

'9 Claims. (01. 260-461) Of this group of lower molecular weight compounds, the p-phenylene compounds in which R represents an aliphatic group, e. 3., methyl, ethyl or p-hydroxyethyl are especially useful as photographic developers in color photography.

Our new compounds can be prepared by reducing the appropriate nitro compounds, 1. e. ni-

tro compounds of the following general formulas:

III

whereinD, R, R, R", R'" and X have the values given above. Such nitro compounds are prepared by condensing nitro-N-hydroxyalkylarylamines with phosphorous chlorides, in accordance with the following chemical equations:

wherein D represents an oand p-arylene group, Q e. g. an oand p-phenylene group, R represents an alkylene group of e. g, ethylene, propylene,

two or more carbon atoms,

etc., R represents hy-.

drogen or an alcohol radical, e. g., methyl, ethyl,

cyclohexyl, benzyl R' each represents group, and X represents oxygen or sulfur.

The compounds the most eflicacio'us p-hydroxyethyl, etc., R" and I hydrogen, a hydroxyl gr p. an alkoxyl group, an alkylthio group or an amino of lower molecular weight are photographic developers, e. g'.,

those in which Drepr'esents an 0- or p-phenylene group, in 'wh'ch It represents ethylene, in which methyl, ethyl or fl-hyand Rf" each 'repre- R represents, hydrogen, droxyethyl and in which 37 sent a hydroiiyl" group, a methoxyl or ethoxyl ethylthio group or an aminogr'oup. Thepphenylene compounds are -gen'erallysiiiierior to the :0

in env n eomm d In these equations D, R, R, R", R?" and X have the values given above.

:As acid-binding agents 'in the above processes,

tertiary amines, e. g., pyridine, vlI-methylpiperidine and dimethylaniline, are advantageously em- ,50 ployed. The condensation of the nitro-N-hydroxyallryl arylam'ines with thephosphorous chlorides is advantageously effected at about, 0 C. Nitro-N-hyciroxyalkylarylamines can be prepared by con n n n c i o l d ocarbons (er a. t w l m ee ene iwmtte o be me. n

4-nitro-1-chloronaphthalene) with hydroxyalkylamines, in accordance with the process described by Kremr-J. Am. Chem. Soc. 61, 1321 (1939). A number of the phosphorous chlorides employed in our invention are well known substances. Dialkyl 5. esters of the monochloride of phosphoric acid can be prepared as described by Wichelhaus-Ann. (suppl.) 6, 264 (1868) Dialkyl esters of the monochloride of dithiophosphoric acid can be similarly prepared employing mercaptans instead oi alcohols.

The nitro compounds can be reduced in any advantageous manner. We have found that the reductions are most advantageously accomplished by hydrogenating the nitro compounds in the presence of Raney nickel.

Alternatively our new phenylenediamine derivatives can be prepared a illustrated in the (a) /C I NH: BIN N\ l 00H; l cnl-cnl-o- Similarly our other phenylenediamine derivatives can be prepared.

The following examples will serve to illustrate further the manner of obtaining our new compounds. These examples are not intended to limit our invention.

Example 1.N-cyclohe:ryl-N-(p-dimethylphosphatoethyl) -p-phenylenediamine maintained at that temperature for one hour. The mixture was then treated with an aqueous solution of 0.15 gram-mole of sodium bicarbonate at 0 for several hours. The water and pyridine were then removed from the mixture under reduced pressure and the resulting yellow crystalline compound was washed with water and dried. The yield was nearly quantitative. This yellow crystalline compound, viz. N-cyclohexyl-N-(fl-dimethylphosphatoethyl)-p-nitroaniline, was dissolved in 200 cc. of methanol. nickel catalyst were mixed with the solution. The resulting mixture was subjected to hydrogenation at 50 C. under a hydrogen pressure oi 1500 pounds. Reduction was complete in about minutes. When cool, the reduction mixture was filtered to remove the nickel, and any desired salt is prepared in the usual manner, viz. by treating the filtered reduction mixture with a molecularly equivalent amount of an acid, e. g. 10 percent sulfuric acid, and concentrating (in vacuo) and chilling until the salt separates out. The free base is not stable in air.

Example 2.-N-ethyl-N- ('y-dimethyldithiophosphatopropyl) -p-phenylenediami7ze 22.4 g. (0.1 mole) of p-nitro-N-ethyl-N-(w-hydroxypropyl) -aniline were dissolved in 500 cc. of dry pyridine. The mixture was cooled to 0 C. To the cooled mixture was added 28.4 g. (0.15 mole) of the dimethyl ester of the monochloride of dithio phosphoric acid having the formula:

0 SCH-z our SCH:

The mixture was worked up as in Example 1 and the resulting product, viz. N-ethyI-N-(y-dL methyldithiophosphatopropyl) p phenylenediamine, was then reduced as in Example 1, and isolated as the sulfate.

Example 3.,N- (fl-phosphatoethyl) -p-phenylenediamine 18.2 g. (0.1 mole) of N-(p-hydroxyethyl) -onitroaniline were dissolved in 250 cc. of pyridine. The mixture was cooled to 0 C. To the cooled mixture were added 18.2 g. (0.12 mole) of phosphorous oxytrichloride, dropwise with stirring, over a period of one hour. The reaction mixture was stirred for four hours and warmed to to C. over a period of two hours and maintained at that temperature for one hour. The mixture was then treated with an aqueous solution of 0.36 gram-mole of sodium bicarbonate at 0 C. for several hours. The water and pyridine were then removed from the mixture under reduced pressure and the resulting yellow crystalline compound was washed and dried. This yellow crystalline compound, viz. N-(p phosphatoethyl) o-nitroeniline, was dissolved in methanol and reduced as in Example 1. The resulting phenylenediamine derivaflve is unstable in air, but white in color when air is excluded.

2 g. of Raney' 19oz), dropwlse with as g. (0.1 mole) o? N-etbyl-N-(B-hydmxyethyll-i-amino-d-nitronaphthalene were dissoiveddnmccoidrypyrldine. Themixturewas coolitoO' C. Tothecooledmixhirewere added 11.1 g. (0.15 mole) of chlorophosphoryl described in Ann. 326, 236, stirring, over a period of mixture was stirred for diamide (prepared as one hour. The reaction four hours and warmed to 50 to C. over a period of two hours and maintained at that temperature for one hour. The mixture was then treated with an aqueous solution of $.15 grammole of sodium bicarbonate at 0 C. for several hours. The waterand pyridine were then removed from the mixture. under reduced pressure and the resulting yellow crystalline compoimd was washed and dried. This yellow crystalline compound, viz. N-ethyl-(N-p-diamidophosphatoethyl) -1,4-naphthaiene was dissolved in methanol and reduced as in Example 1 to give the naphthylenediamine derivative.

Example 5.lV-ethyl N -(p-dimetnylpnos hatoethyl) -1,4-diamino-Z-methylbenzene 7 00H: '21:; g. (0.1 mole) of N-ethyl-N-(p-dimethylphosphatoethyl) -m-toluidine (prepared from N- ethyl-N-(p-hydroxyethyl) -m-toluidine and the dimethyl ester of the monochloride of phosphoric acid according to the process ample 1) were dissolved in 200 cc. of cold acetic acid. To the cold solution were added 0.1 grammole of o-chlorobenzene diazonium chloride. The coupling was completed by the addition of sodium bicarbonate. The azo compound was precipitated from thereaction mixture by the addition or water. The precipitated azo compound was filtered of! and washed free from acid. The azo compound was dissolved in methanol and hydrogenated in the presence of Raney nickel. The resulting reduction mixture was filtered to remove the nickel. The methanol was removed by distillation under reduced pressure and the residuevwas steam aniline. The residue was treated with sulfuric acid to convert the phenylenediamine derivative to zlele sulfate which was then recrystallized from wa r.

Example 6 .N-eth1ll N -(pphosphitoethyl) -p- I phenylenediamine 22.1 g. (0.1 mole) of N-ethyl-N-(p-hydroxy- .ethyl) -p-nitroaniline were dissolved in 500 cc. oi

dry pyridine. To the cooled mole) of phosphorous stirring, over a period of one hour.

described in Exdistilled to remove o-chloro-.

maintained at flilt was warmed toiO'toU'Qoveraperlodof 710F318 hour.

'fliemixturewasthmtreatedwlth-anoqmus solution or 0.45 gram-mole or sodium bicarbonate peciallv adapted to use in color photography (see -above) can be used to develop visible images from latent images in'silverhalide emulsions or to develop silver images from silver halide images which are obtained by a so-called reversal process or by rehalogenizing a visible silver image. when employed in connection with color photog-' raphy, the phenylenediamine derivatives act as developers in the presence of couplers and the oxidation products of the phenylenediamine derivatives, arising from the developing action. couple with the couplers or color-formers to give colored bodies or dyes. When used for the formation of colored photographic images, the phenylenediamine derivatives can be used in conjunction with any well known coupler compounds. such as those described in Fischer U. S. Patent 1,102,028, dated June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602, dated February 15, 1938; Mannes, Godowsky and Peterson U. S. Patent 2,115,934, dated April 26, 1938; and Mannes, Godowsky and Peterson U. S. Patent 2,126,337, dated August 9, 1938.

All the phenylenediamine derivatives described herein can be used for the purpose of produc- 'ing black-and-white images from exposed photographic silver halide emulsions.

Developing solutions comprising our new phenylenediamine derivatives can be made up in the usual manner, using sodium sulfite and sodium carbonate.

The term alcohol radical, in accordance with customary usage, is intended to mean an or-- I ganic radical, which corresponds to an alcohol and is derived therefrom by dropping the hydroxyl group, e. g., n-propyl is derived from n-propyl alcohol by dropping the OH group.

benzyl is derived from benzyl alcohol by dropping the OH group, and tertiary butyl is derived by dropping the OH group from tertiary butyl alwho].

We claim:

1. A compound characterized by the following general formula:

HzN-D-N a-o-P- RI! wherein D represents a member selected from the group consisting of o-arylene and p-arylene groups, It represents an alkylene group having at leasttwo carbon atoms, R represent a member selected from the group consisting of hydrogen and alcohol radicals, R" represents a, member selected from the group consistingoi hydrofll 8,411,587 1 e I e o ilolthe'fmmg smmsamxts mmmeanmh: m mflfomenmdmm. A mpound of the following M 120 wherein R an While 8 ml having flflo mp: Ind amino,

at least two carbon atoms, R represents a mem- A of the foam! mm'mh: ber selected farm the group'consisting of hydrom 7 gen and alcohol radicals, R" mpresent a mm- 1 NH N 0 but selected from the group consisting of hy- I at droxyl gmups, alkoxyl groups, alkylthio groups on I d amino groups. mm

3. A compound of the following general Ior- 7. A oompmmd of the 1 formula: mula: m H

O K (whom-0d f B-'OZPR" cm H I V on I B 2 8. A mom of the f :Iorwherein R represents an alky'lene gmcmp having at least two carbon atoms, R represents a member 7 n selected imm the group consisting of hydrogen Q and aliphatic R represents a member ill selected from the group consisting of 'hydroxyl M 1 groups, lthio groups and EFWPS- wherein R W n o is an :ah 1 gm and R" L A mmpmmd the f0Euwmg general mepzresentsamembersebcbedfmmihegmupcm- 1 1m: 35 of :a. hydroxyl emai y [3w kylthio and amino groups. m 0 9. A compound of the following I I onrom-mi -n" Elm I e L wherein R represents an alkyd group and R v remesents a member selected from the group rcon- Sistine of hyfimxyl r p xyl r ups, al- JOSEPH B. DIQKEY. kylth'o groups and amino emu 45 JAMES G. MEHMILYQ 

